We have developed new synthetic methods which we will apply to the total synthesis of the antineoplastic agent daunomycin. Plans for the total synthesis of cytotoxic sesquiterpene lactones damsin, helenalin and quadrone are also presented. In the sesquiterpene related work, we will develop a method of carbocyclic ring synthesis that is functionally equivalent to an intramolecular Diels-Alder reaction between a carbene and a diene system. Model studies will feature an efficient, stereospecific total synthesis of the sesquiterpene longifolene.